CN111500029A - Bio-based degradable knife and fork material and preparation method thereof - Google Patents

Bio-based degradable knife and fork material and preparation method thereof Download PDF

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CN111500029A
CN111500029A CN202010382890.2A CN202010382890A CN111500029A CN 111500029 A CN111500029 A CN 111500029A CN 202010382890 A CN202010382890 A CN 202010382890A CN 111500029 A CN111500029 A CN 111500029A
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parts
knife
bio
auxiliary agent
antioxidant
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孟庆栓
吕敬先
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Shenzhen Guozhi New Material Technology Co ltd
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Shenzhen Guozhi New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

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Abstract

The invention discloses a bio-based degradable knife and fork material and a preparation method thereof, wherein the bio-based degradable knife and fork material is prepared from the following raw materials: straw fiber, plant starch, aliphatic polyester, sodium montmorillonite, hydrophobic auxiliary agent, thermoplastic auxiliary agent, composite nucleating agent and functional auxiliary agent. The bio-based degradable knife and fork material can be automatically decomposed within 135 days, so that the environmental pollution is avoided, and the manufacturing cost is greatly reduced; the main raw material of the bio-based degradable knife and fork material is straw, and the straw is used for preparing the degradable material, so that the problem of difficult straw utilization can be effectively solved, and waste is changed into valuable; the bio-based degradable knife and fork material can effectively utilize the high toughness strength and the thermoplastic property of the plant fiber by blending and modifying the straw fiber and the plant starch, and then the modified sodium-based montmorillonite is combined to form an intercalation structure in the straw fiber and the plant starch material, so that the impact strength, the toughness and the heat resistance are obviously improved.

Description

Bio-based degradable knife and fork material and preparation method thereof
Technical Field
The invention relates to the technical field of degradable knife and fork articles, in particular to a bio-based degradable knife and fork material and a preparation method thereof.
Background
China is a large country for producing grains, and the straws are generally incinerated in rural areas in various regions for a long time. According to rough statistics, the straws burned in China account for about 30% of the total storage amount, and waste gas caused by burning the straws seriously pollutes air. In recent years, China frequently generates a large-range deep haze, and the problem of solving the deep haze is very slow. The related data show that the total grain yield is 6.1 hundred million tons and the straw yield is about 8 hundred million tons in China, and the straw yield is increased by 1200 million tons every year along with the increase of the grain yield. The straw is used as a byproduct in the production of grain crops and economic crops, contains rich protein, vitamins, nitrogen, phosphorus, potassium, trace elements and the like, and can be used for extracting energy sources such as alcohol, bio-gasoline, pyroligneous acid, wood tar, polyoligosaccharide and the like, pesticides, food raw materials, additives, carbon products, forage grass and the like. Taking corn stalks as an example, about 1 ton of stalks can be produced in one mu of land, and about 500 kg of compound fertilizer, 400 kg of paper pulp and 100 kg of alcohol can be produced through comprehensive utilization. The comprehensive utilization of the straws is well done, and the effects of 'doing little work' on agriculture and grain production in China can be achieved from 'burning prohibition' to comprehensive utilization to industrialization, so that the social benefits are far more profound.
As is well known, white pollution is continuously destroying the environment which we rely on to live in the present, and people are struggling to eliminate the harm brought by the white pollution in the world, and flood disasters are caused by the fact that many good fields reduce production, land desertification and river blockage.
Takeaway has become the normal state of life of most people, the demand of disposable cutlery of carriers for takeaway is more and more great, the big data report of takeaway in China in 2017, the income of big catering dish reaches 39644 million yuan, it is expected to keep the acceleration rate of about 10% in the future, the income of three official platforms of takeaway in China in 2107 year reaches 3000 million yuan, the three official platforms of beautiful groups, hungry and hundred degrees show, about 6000 million takeaway are distributed in the avenue and the lane every day, this means that about 10 tons of plastic cutlery are produced every day, these plastic cutlery need last one hundred years of time after being abandoned or buried, can degrade, the pollution to the environment is very serious, waste to the resource is more serious.
In the process of preparing the polymer-based montmorillonite nanocomposite, because the interlayer distance of montmorillonite is only about 1nm, and the interlaminar chemical microenvironment is hydrophilic and oleophobic, the intercalation of monomers or macromolecules is not facilitated. Montmorillonite generally needs to be organically modified before use. In order to make the polymer intercalate and exfoliate the montmorillonite well, organic cation compounds such as organic quaternary ammonium salt and phosphonium salt or other organic matters with montmorillonite-philic functional groups such as hydroxyl, amino and the like are generally used for modifying the montmorillonite, so that the montmorillonite and the polymer body have good compatibility and high thermal stability. For example, in the polymer-based layered silicate clay nanocomposite, hydrophilic layered clay needs to be modified by fatty amine surfactants to ensure compatibility with the polymer, thereby improving the gas barrier property, mechanical properties, thermal stability, flame retardancy and the like of the material. The organic treatment of montmorillonite usually adopts small molecular quaternary ammonium salt to exchange with montmorillonite ion, and various organic cations can replace original hydrated cations between montmorillonite layers through ion exchange reaction, i.e. cations between clay layers exchange with organic cations to form lipophilic clay.
The price of polylactic acid P L A, polycaprolactone P L A, polyvinyl alcohol, polyhydroxyalkanoate and polybutylene succinate in polyester is higher, the price of the produced disposable biodegradable knife is 1-2 times higher than that of the market, and the disposable biodegradable knife cannot be any by consumers and merchants.
Therefore, people can improve the performance of the resin to a certain extent and improve the utilization of straw resources through the research of adding biodegradable high molecular compounds into the straw powder. At present, the material taking straws as the raw material has poor heat resistance, and the impact strength and the toughness of the material can not meet the requirements. In view of the above, a need exists for a biodegradable straw powder material which can solve the problems of poor heat resistance, impact strength and toughness of the existing biodegradable straw powder material through a process formula.
Disclosure of Invention
The invention provides a bio-based degradable knife and fork material and a preparation method thereof, wherein the bio-based degradable knife and fork material can be biodegraded, and the impact strength, the toughness and the heat resistance are obviously improved by blending and modifying straw fibers and plant starch and then combining modified sodium-based montmorillonite to form an intercalation structure in the straw fibers and plant starch materials.
The invention adopts the following technical scheme for solving the technical problems:
a bio-based degradable knife and fork material is prepared from the following raw materials in parts by weight: 8-25 parts of straw fiber, 8-25 parts of plant starch, 10-60 parts of aliphatic polyester, 1-6 parts of sodium-based montmorillonite, 1-6 parts of hydrophobic auxiliary agent, 4-12 parts of thermoplastic auxiliary agent, 1-6 parts of composite nucleating agent and 1-6 parts of functional auxiliary agent.
As a most preferable scheme, the bio-based degradable knife and fork material is prepared from the following raw materials in parts by weight: 15 parts of straw fiber, 15 parts of plant starch, 30 parts of aliphatic polyester, 3 parts of sodium montmorillonite, 2 parts of hydrophobic auxiliary agent, 8 parts of thermoplastic auxiliary agent, 4 parts of composite nucleating agent and 3 parts of functional auxiliary agent.
As a preferable scheme, the straw fiber is one or more of corn straw fiber, wheat straw fiber, soybean straw fiber, bran fiber, rice hull fiber and wood fiber.
As a most preferable scheme, the straw fiber is corn straw fiber and wheat straw fiber which are mixed according to the weight ratio of 1:1.
Preferably, the plant starch is one or more of potato starch, corn starch, wheat starch, tapioca starch and taro starch.
As a most preferred embodiment, the plant starch is corn starch.
As a preferred scheme, the sodium-based montmorillonite is modified sodium-based montmorillonite, and the preparation method of the modified sodium-based montmorillonite comprises the following steps: adding 50-70 parts of ethanol into 80-120 parts of deionized water to prepare an ethanol water solution, adding 10-20 parts of sodium montmorillonite into the ethanol water solution, carrying out ultrasonic treatment for 15-25 min to form a stable suspension solution, adding octadecyl dimethyl tertiary amine according to the cation exchange capacity of 60-80 mmol/100g of sodium montmorillonite, fully reacting, washing for 2-4 times by using ethanol, drying, and grinding to obtain the modified sodium montmorillonite.
In a preferable embodiment, the aliphatic polyester is one or two of polylactic acid and polybutylene succinate.
As a most preferred embodiment, the aliphatic polyester is polybutylene succinate.
Preferably, the hydrophobic auxiliary agent is one or more of vinyltriethoxysilane, KH-570, KH-550, KH-560, KH-590, isopropyl triisostearoyl titanate, isopropyl trioleoyl titanate, dodecylbenzenesulfonyl, peanut oil, an aluminate coupling agent, an aluminum-titanium composite coupling agent and stearic acid.
As a most preferable scheme, the hydrophobic auxiliary agent is vinyl triethoxysilane, KH-570 according to the weight ratio of 1: 2 and mixing.
Preferably, the thermoplastic auxiliary agent is one or more of 1, 4-butanediol, 2, 5-hexanediol, glycerol, ethylene glycol, propylene glycol, sorbitol, xylitol, maltitol, formamide and acetamide.
As a most preferred option, the thermoplastic adjuvant is sorbitol.
As a preferable scheme, the composite nucleating agent is two or more of nano talcum powder, nano light calcium carbonate, TMC-200, TMC-210, TMC-300, TMC-306, TMC-328, K L-4300, K L-4376 and K L4370B.
As a most preferable scheme, the composite nucleating agent is nano talcum powder, TMC-328 according to the weight ratio of 1: 1.5 mixing.
Preferably, the functional auxiliary agent is one or more of a lubricant, an antioxidant and a toughening compatibility auxiliary agent.
As a most preferable scheme, the functional auxiliary agent is prepared from a lubricant, an antioxidant and a toughening compatibility auxiliary agent according to a weight ratio of 1:1: 1.
Preferably, the lubricant is one or more of fatty acid amides, liquid paraffin, solid paraffin, microcrystalline paraffin, polyethylene wax, polytetrafluoroethylene wax and fatty acid.
As a most preferred solution, the lubricant is liquid paraffin.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 622, antioxidant 215, antioxidant B561, antioxidant BHT, antioxidant T502, antioxidant DSTOP and vitamin E.
As a most preferred embodiment, the antioxidant is antioxidant 1010.
Preferably, the toughening compatibility auxiliary agent is one or more of linear polyethylene, EVA resin, AX8900, EAA, maleic anhydride grafted resin, starch-based aliphatic polyester grafted copolymer and starch-ethylene monomer grafted copolymer.
As a most preferred scheme, the toughening compatibility auxiliary agent is linear polyethylene.
The invention also provides a preparation method of the bio-based degradable knife and fork material, which comprises the following steps:
(1) drying the straw fiber and the plant starch, weighing the raw materials according to the proportion, adding the straw fiber, the plant starch, the sodium montmorillonite and the hydrophobic auxiliary agent into a high-speed mixer, and uniformly mixing;
(2) adding a thermoplastic auxiliary and a functional auxiliary into a high-speed mixer, wherein the temperature of the high-speed mixer is 80-100 ℃, the rotating speed is 2000-3000 r/min, and the mixing time is 10-30 min;
(3) adding aliphatic polyester and a composite nucleating agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 80-100 ℃, the rotating speed is 800-1200 r/min, the mixing time is 5-10 min, the temperature is reduced to 60-65 ℃, then the materials are mixed for 5-10 min, and cooling is carried out to obtain a mixture;
(4) and pouring the mixture into a double-screw machine for melt extrusion, setting the temperature of each section, wherein the temperature of the front section and the temperature of the rear section are both set to be 130-145 ℃, the temperature of the middle section is set to be 145-165 ℃, and then, performing material manufacturing through an air-cooled drag chain type double-screw granulator to obtain the bio-based degradable knife and fork material.
As a preferable scheme, the temperature of the high-speed mixer in the step (1) is 90-110 ℃, the rotating speed is 1000-1500 r/min, and the mixing time is 10-20 min.
The invention has the beneficial effects that: (1) the bio-based degradable knife and fork material is prepared from straw fibers, plant starch, aliphatic polyester, sodium montmorillonite, a hydrophobic auxiliary agent, a thermoplastic auxiliary agent, a composite nucleating agent and a functional auxiliary agent, can be automatically decomposed within 135 days, cannot cause environmental pollution, and has greatly reduced manufacturing cost compared with plastics; (2) the main raw material of the bio-based degradable knife and fork material is straw, and the degradable material is prepared from straw, so that the problem of difficult straw utilization can be effectively solved, waste materials are changed into valuable materials, and air pollution caused by the combustion of waste gas and straw at present can be effectively solved; (3) according to the bio-based degradable knife and fork material, the straw fiber and the plant starch are blended and modified, so that the high toughness strength and the thermoplastic property of the plant fiber can be effectively utilized, and then the modified sodium-based montmorillonite is combined to form an intercalation structure in the straw fiber and the plant starch material, so that the impact strength, the toughness and the heat resistance are remarkably improved; and (4) the interlayer spacing of the modified sodium-based montmorillonite is remarkably improved by modification, and the comprehensive performance of the modified sodium-based montmorillonite is remarkably improved by modifying the modified sodium-based montmorillonite by using specific octadecyl dimethyl tertiary amine, so that the modified sodium-based montmorillonite has better compatibility, thermal stability and mechanical property.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention, and the parts described in the present invention are all parts by weight.
Example 1
A bio-based degradable knife and fork material is prepared from the following raw materials in parts by weight: 15 parts of straw fiber, 15 parts of plant starch, 30 parts of aliphatic polyester, 3 parts of sodium montmorillonite, 2 parts of hydrophobic auxiliary agent, 8 parts of thermoplastic auxiliary agent, 4 parts of composite nucleating agent and 3 parts of functional auxiliary agent.
The straw fiber is formed by mixing corn straw fiber and wheat straw fiber according to the weight ratio of 1:1.
The plant starch is corn starch.
The aliphatic polyester is poly butylene succinate.
The hydrophobic auxiliary agent is vinyl triethoxysilane, KH-570 in a weight ratio of 1: 2 and mixing.
The thermoplastic auxiliary agent is sorbitol.
The composite nucleating agent is nano talcum powder and TMC-328 according to the weight ratio of 1: 1.5 mixing.
The functional auxiliary agent is prepared from a lubricant, an antioxidant and a toughening compatibility auxiliary agent according to the weight ratio of 1:1: 1.
The lubricant is liquid paraffin; the antioxidant is antioxidant 1010.
The toughening compatibility auxiliary agent is linear polyethylene.
The preparation method of the bio-based degradable knife and fork material comprises the following steps:
(1) drying straw fibers and plant starch, weighing the raw materials according to a ratio, adding the straw fibers, the plant starch, sodium montmorillonite and a hydrophobic auxiliary agent into a high-speed mixer, and uniformly mixing, wherein the temperature of the high-speed mixer is 100 ℃, the rotating speed is 1200r/min, and the mixing time is 15 min;
(2) adding a thermoplastic auxiliary agent and a functional auxiliary agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 90 ℃, the rotating speed is 2500 r/min, and the mixing time is 20 min;
(3) adding aliphatic polyester and a composite nucleating agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 90 ℃, the rotating speed is 2500 r/min, the mixing time is 8min, the temperature is reduced by 62 ℃, then mixing is carried out for 8min, and cooling is carried out to obtain a mixture;
(4) and pouring the mixture into a double-screw machine for melt extrusion, setting the temperature of each section, wherein the temperature of the front section and the temperature of the rear section are both set to be 130-145 ℃, the temperature of the middle section is set to be 145-165 ℃, and then, performing material manufacturing through an air-cooled drag chain type double-screw granulator to obtain the bio-based degradable knife and fork material.
Example 2
A bio-based degradable knife and fork material is prepared from the following raw materials in parts by weight: 20 parts of straw fiber, 20 parts of plant starch, 50 parts of aliphatic polyester, 5 parts of sodium montmorillonite, 5 parts of hydrophobic auxiliary agent, 8 parts of thermoplastic auxiliary agent, 4 parts of composite nucleating agent and 3 parts of functional auxiliary agent.
The straw fiber is corn straw fiber.
The plant starch is potato starch and corn starch in a weight ratio of 1:1 and mixing.
The aliphatic polyester is poly butylene succinate.
The hydrophobic auxiliary agent is vinyl triethoxysilane, KH-550 in a weight ratio of 1: 1.2 mixing.
The thermoplastic auxiliary agent is 1, 4-butanediol.
The composite nucleating agent is prepared by mixing nano-scale light calcium carbonate and K L-4300 according to a weight ratio of 1-1.5.
The functional auxiliary agent is composed of a lubricant, an antioxidant and a toughening compatibility auxiliary agent according to the weight ratio of 1:1: 1.
The lubricant is solid paraffin; the antioxidant is antioxidant DSTOP; the toughening compatilizer auxiliary agent is AX 8900.
The preparation method of the bio-based degradable knife and fork material comprises the following steps:
(1) drying straw fibers and plant starch, weighing the raw materials according to a ratio, adding the straw fibers, the plant starch, sodium montmorillonite and a hydrophobic auxiliary agent into a high-speed mixer, and uniformly mixing, wherein the temperature of the high-speed mixer is 100 ℃, the rotating speed is 1200r/min, and the mixing time is 15 min;
(2) adding a thermoplastic auxiliary agent and a functional auxiliary agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 90 ℃, the rotating speed is 2500 r/min, and the mixing time is 20 min;
(3) adding aliphatic polyester and a composite nucleating agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 90 ℃, the rotating speed is 2500 r/min, the mixing time is 8min, the temperature is reduced by 62 ℃, then mixing is carried out for 8min, and cooling is carried out to obtain a mixture;
(4) and pouring the mixture into a double-screw machine for melt extrusion, setting the temperature of each section, wherein the temperature of the front section and the temperature of the rear section are both set to be 130-145 ℃, the temperature of the middle section is set to be 145-165 ℃, and then, performing material manufacturing through an air-cooled drag chain type double-screw granulator to obtain the bio-based degradable knife and fork material.
Example 3
The bio-based degradable knife and fork material is characterized by being prepared from the following raw materials in parts by weight: 8 parts of straw fiber, 8 parts of plant starch, 10 parts of aliphatic polyester, 1 part of sodium montmorillonite, 1 part of hydrophobic auxiliary agent, 4 parts of thermoplastic auxiliary agent, 1 part of composite nucleating agent and 1 part of functional auxiliary agent.
The straw fiber is formed by mixing corn straw fiber and soybean straw fiber according to the weight ratio of 1: 1.6.
The plant starch is prepared by mixing potato starch, corn starch and wheat starch according to the weight ratio of 1:1: 1.
The aliphatic polyester is prepared by mixing polylactic acid and polybutylene succinate according to a weight ratio of 1-0.5.
The hydrophobic auxiliary agent is KH-550.
The thermoplastic auxiliary agent is maltitol.
The composite nucleating agent is prepared by mixing nano talcum powder and TMC-210 according to the weight ratio of 1-0.8.
The functional auxiliary agent is a lubricant, an antioxidant and a toughening compatibility auxiliary agent according to the weight ratio of 1:1: 1.
The lubricant is polyethylene wax; the antioxidant is antioxidant BHT; the toughening compatilizer auxiliary agent is AX 8900.
The preparation method of the bio-based degradable knife and fork material comprises the following steps:
(1) drying straw fibers and plant starch, weighing the raw materials according to a ratio, adding the straw fibers, the plant starch, sodium montmorillonite and a hydrophobic auxiliary agent into a high-speed mixer, and uniformly mixing, wherein the temperature of the high-speed mixer is 100 ℃, the rotating speed is 1200r/min, and the mixing time is 15 min;
(2) adding a thermoplastic auxiliary agent and a functional auxiliary agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 90 ℃, the rotating speed is 2500 r/min, and the mixing time is 20 min;
(3) adding aliphatic polyester and a composite nucleating agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 90 ℃, the rotating speed is 2500 r/min, the mixing time is 8min, the temperature is reduced by 62 ℃, then mixing is carried out for 8min, and cooling is carried out to obtain a mixture;
(4) and pouring the mixture into a double-screw machine for melt extrusion, setting the temperature of each section, wherein the temperature of the front section and the temperature of the rear section are both set to be 130-145 ℃, the temperature of the middle section is set to be 145-165 ℃, and then, performing material manufacturing through an air-cooled drag chain type double-screw granulator to obtain the bio-based degradable knife and fork material.
Example 4
Example 4 differs from example 1 in that the sodium montmorillonite described in example 4 is a modified sodium montmorillonite, and the other is the same.
Adding 60 parts of ethanol into 100 parts of deionized water to prepare an ethanol water solution, adding 15 parts of sodium montmorillonite into the ethanol water solution, carrying out ultrasonic treatment for 20min to form a stable suspension solution, adding octadecyl dimethyl tertiary amine according to the cation exchange capacity of 70mmol/100g of sodium montmorillonite, carrying out full reaction, washing for 3 times by using ethanol, drying, and grinding to obtain the modified sodium montmorillonite.
Comparative example 1
Comparative example 1 is different from example 4 in that the preparation method of the bio-based degradable cutlery material is different, and the others are the same.
The preparation method of the bio-based degradable knife and fork material comprises the following steps:
(1) drying straw fibers and plant starch, weighing raw materials according to a ratio, adding the straw fibers, the plant starch, sodium montmorillonite, a hydrophobic auxiliary agent, a thermoplastic auxiliary agent, a functional auxiliary agent, aliphatic polyester and a composite nucleating agent into a high-speed mixer, and uniformly mixing, wherein the temperature of the high-speed mixer is 100 ℃, the rotating speed is 1200r/min, and the mixing time is 45 min; after the material mixing is finished, cooling to obtain a mixture;
(2) and pouring the mixture into a double-screw machine for melt extrusion, setting the temperature of each section, wherein the temperature of the front section and the temperature of the rear section are both set to be 130-145 ℃, the temperature of the middle section is set to be 145-165 ℃, and then, performing material manufacturing through an air-cooled drag chain type double-screw granulator to obtain the bio-based degradable knife and fork material.
Comparative example 2
Comparative example 2 differs from example 4 in that comparative example 2 does not contain vegetable starch, and is otherwise identical.
Comparative example 3
Comparative example 3 differs from example 4 in that comparative example 3 does not contain modified sodium montmorillonite, and the other is the same.
Comparative example 4
Comparative example 4 is different from example 4 in that the modified sodium-based montmorillonite described in comparative example 5 is prepared by the same method as example 4.
The sodium-based montmorillonite is modified sodium-based montmorillonite, and the preparation method of the modified sodium-based montmorillonite comprises the following steps: adding 60 parts of ethanol into 100 parts of deionized water to prepare an ethanol water solution, adding 15 parts of sodium-based montmorillonite into the ethanol water solution, carrying out ultrasonic treatment for 20min to form a stable suspension solution, adding diallyl methyl octadecyl ammonium bromide according to the cation exchange capacity of 70mmol/100g of sodium-based montmorillonite, carrying out full reaction, washing for 3 times by using ethanol, drying, and grinding to obtain the modified sodium-based montmorillonite.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the impact strength of the material is measured according to GB/T1043.1-2008, the high temperature resistance is measured according to GB/T1634-2004, the elongation at break is measured according to GB/T16421-1996, and the measurement results are shown in Table 1.
TABLE 1 test values
Figure 608284DEST_PATH_IMAGE001
As can be seen from Table 1, the bio-based degradable cutlery material of the invention has good notch impact strength, heat resistance and toughness, wherein example 4 has the best notch impact strength, heat resistance and toughness; compared with the examples 1 to 3, the raw materials and the proportion thereof in the invention have different proportions and the selection of the raw materials can influence the notch impact strength, the heat resistance and the toughness, wherein the example 1 is the best proportion and the selection of the raw materials, and the modified sodium-based montmorillonite can obviously improve the notch impact strength, the heat resistance and the toughness compared with the examples 1 and 4; comparing example 4 with comparative example 1, it can be seen that the notch impact strength, heat resistance, and toughness are significantly reduced after the preparation method of the bio-based degradable cutlery material of the present invention is replaced, and it can be seen that the preparation method of the bio-based degradable cutlery material of the present invention has certain characteristics; comparing example 4 with comparative example 2, it can be seen that the plant fiber of the present invention can significantly improve notched impact strength, heat resistance, and toughness of the material; comparing example 1 with comparative examples 3-4, it can be seen that the modified sodium-based montmorillonite can significantly improve the notch impact strength, heat resistance and toughness of the material; when the modified sodium-based montmorillonite is replaced, the notch impact strength, heat resistance and toughness of the material are obviously reduced.
2. The biodegradation performance test comprises the steps of injecting the product by a 300 g injection machine to obtain standard sample strips with the size of 100 mm × 10 mm × 1.0.0 mm, carrying out various performance tests on the standard sample strips by adopting the following standard methods, wherein the test results are shown in the following table 2, weighing and recording the weight of each standard sample strip at the moment, wrapping the standard sample strips among gauzes respectively, burying the standard sample strips in flower garden soil 20 cm away from the ground, taking out the standard sample strips after 60 days, cleaning, drying, weighing and recording the weight, and calculating the weight loss ratio (%) (the weight loss ratio of the standard sample strips is (the weight before the test-the weight after the standard sample strips are buried in the soil 60 days)/the weight before the test is × 100%, and the days required after the complete degradation is tested, wherein the weight loss ratio reaches 98%, and the standard sample strips are regarded as complete.
TABLE 2 biodegradability test
Figure 184758DEST_PATH_IMAGE002
As can be seen from table 2, the material according to the invention is capable of degrading 81.5% in 60 days and completely within 135 days.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. The bio-based degradable knife and fork material is characterized by being prepared from the following raw materials in parts by weight: 8-25 parts of straw fiber, 8-25 parts of plant starch, 10-60 parts of aliphatic polyester, 1-6 parts of sodium-based montmorillonite, 1-6 parts of hydrophobic auxiliary agent, 4-12 parts of thermoplastic auxiliary agent, 1-6 parts of composite nucleating agent and 1-6 parts of functional auxiliary agent.
2. The bio-based degradable knife and fork material as claimed in claim 1, wherein the bio-based degradable knife and fork material is prepared from the following raw materials in parts by weight: 15 parts of straw fiber, 15 parts of plant starch, 30 parts of aliphatic polyester, 3 parts of sodium montmorillonite, 2 parts of hydrophobic auxiliary agent, 8 parts of thermoplastic auxiliary agent, 4 parts of composite nucleating agent and 3 parts of functional auxiliary agent.
3. The bio-based degradable knife and fork material as claimed in claim 1, wherein the straw fiber is one or more of corn straw fiber, wheat straw fiber, soybean straw fiber, rice bran fiber, rice hull fiber, and wood fiber; the plant starch is one or more of potato starch, corn starch, wheat starch, cassava starch and taro starch.
4. The bio-based degradable knife and fork material as claimed in claim 1, wherein the sodium-based montmorillonite is modified sodium-based montmorillonite, and the preparation method of the modified sodium-based montmorillonite is as follows: adding 50-70 parts of ethanol into 80-120 parts of deionized water to prepare an ethanol water solution, adding 10-20 parts of sodium montmorillonite into the ethanol water solution, carrying out ultrasonic treatment for 15-25 min to form a stable suspension solution, adding octadecyl dimethyl tertiary amine according to the cation exchange capacity of 60-80 mmol/100g of sodium montmorillonite, fully reacting, washing for 2-4 times by using ethanol, drying, and grinding to obtain the modified sodium montmorillonite.
5. The bio-based degradable knife and fork material as claimed in claim 1, wherein the aliphatic polyester is one or two of polylactic acid and polybutylene succinate; the hydrophobic auxiliary agent is one or more of vinyltriethoxysilane, KH-570, KH-550, KH-560, KH-590, triisostearoyl isopropyl titanate, trioleoyl isopropyl titanate, dodecylbenzenesulfonyl, peanut oil, an aluminate coupling agent, an aluminum-titanium composite coupling agent and stearic acid.
6. The bio-based degradable knife and fork material as claimed in claim 1, wherein the thermoplastic auxiliary agent is one or more of 1, 4-butanediol, 2, 5-hexanediol, glycerol, ethylene glycol, propylene glycol, sorbitol, xylitol, maltitol, formamide and acetamide, and the composite nucleating agent is two or more of nano talc, nano light calcium carbonate, TMC-200, TMC-210, TMC-300, TMC-306, TMC-328, K L-4300, K L-4376 and K L4370B.
7. The bio-based degradable knife and fork material of claim 1, wherein the functional additive is one or more of a lubricant, an antioxidant, and a toughening compatibilizer.
8. The bio-based degradable knife and fork material of claim 7, wherein the lubricant is one or more of fatty acid amides, liquid paraffin, solid paraffin, microcrystalline paraffin, polyethylene wax, polytetrafluoroethylene wax, fatty acid; the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 622, antioxidant 215, antioxidant B561, antioxidant BHT, antioxidant T502, antioxidant DSTOP and vitamin E; the toughening compatibility auxiliary agent is one or more of linear polyethylene, EVA resin, AX8900, EAA, maleic anhydride grafted resin, starch-based aliphatic polyester graft copolymer and starch-ethylene monomer graft copolymer.
9. The method for preparing a biodegradable knife and fork material according to any one of claims 1 to 8, which comprises the following steps:
(1) drying the straw fiber and the plant starch, weighing the raw materials according to the proportion, adding the straw fiber, the plant starch, the sodium montmorillonite and the hydrophobic auxiliary agent into a high-speed mixer, and uniformly mixing;
(2) adding a thermoplastic auxiliary and a functional auxiliary into a high-speed mixer, wherein the temperature of the high-speed mixer is 80-100 ℃, the rotating speed is 2000-3000 r/min, and the mixing time is 10-30 min;
(3) adding aliphatic polyester and a composite nucleating agent into a high-speed mixer, wherein the temperature of the high-speed mixer is 80-100 ℃, the rotating speed is 800-1200 r/min, the mixing time is 5-10 min, the temperature is reduced to 60-65 ℃, then the materials are mixed for 5-10 min, and cooling is carried out to obtain a mixture;
(4) and pouring the mixture into a double-screw machine for melt extrusion, setting the temperature of each section, wherein the temperature of the front section and the temperature of the rear section are both set to be 130-145 ℃, the temperature of the middle section is set to be 145-165 ℃, and then, performing material manufacturing through an air-cooled drag chain type double-screw granulator to obtain the bio-based degradable knife and fork material.
10. The preparation method of the bio-based degradable knife and fork material according to claim 9, wherein the temperature of the high-speed mixer in the step (1) is 90-110 ℃, the rotating speed is 1000-1500 r/min, and the mixing time is 10-20 min.
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CN112126202A (en) * 2020-09-30 2020-12-25 梁亚正 High-flame-retardancy color master batch and preparation method thereof
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